N.

DARABIHA Gnralits sur la cintique de combustion

Samedi 29 Mai 2010, 11h00 12h30

Laboratoire d'Energtique Molculaire et Macroscopique, Combustion

ECOLE CENTRALE PARIS

Nasser DARABIHA
nasser.darabiha@em2c.ecp.fr http://www.em2c.ecp.fr Tlphone : +33 1 41 13 10 72 Tlcopie : +33 1 47 02 80 35
1

Fluid Mechanics

Chemical Kinetics

Ther

mody

nami

cs

Combustion
t r o p s n a a n r e T m o n e h P
2

l u M

h p ti-

e s a

w o fl

Why Chemical Kinetics?

Production and destruction of pollutants Ignition, Extinction, Flame Structure, ..

Reacting mixture

Temperature

Collisions

Reaction

CONTENTS
- Some Definitions - Thermodynamics - Chemical kinetics
Arrhenius Law Reaction rate Chemkin

- Reaction mechanism
H2/O2 combustion

- 0-D formulation
Auto-ignition PSR

- Pollutants in atmosphere

Mixing of N species inside a volume nk moles of species k ,

1 mole = 6,02252*1023 molecules
N N

n=

n
k=1 k=1

mass :

m=

k=1

m = n
k

k Mk

mk Mass fraction Yk = m Mk Yk = X k M !

nk Mole fraction X k = n

m Mixture Molar mass M = Xk Mk = k=1 n ! 6

nk Concentration Ck = V
Density

n " Ck = V # 1 k =1

mk "k= V
N

nk M k "k = = Ck M k V !
Mass fraction

" = # "k
k =1

mk "k Yk = = " ! m
7

Stoichiometric reaction Enough oxidant O to burn all fuel F

FF + O O + N2 Products mass stoichiometric coefcient

stoichiometric coefcient

F + S O + N2

Products
8

Stoichiometric reactions:
CnHm + (n+m/4) (O2 + N2) nCO2 +(m/2) H2O + (n+m/4) N2

CH4 + 2 (O2 + N2) C3H8 + 5 (O2 + N2) H2 + 1/2 (O2 + N2)

CO2 +2 H2O + 2 N2 3CO2 +4 H2O + 5 N2 H2O + 1/2 N2

Mixture equivalence ratio

Stoichiometric reaction:
CH4 + S (O2 + N2) Products

Any reaction ... :

CH4 + S( O2 + N2) XCH4 Products

Mixture equivalence ratio

XO2

XCH4 XO2

Stoich

1 S " S = = 1 S" S
10

Any reaction ... :

S CH4 + S (O2 + N2) S"
Products

CH4 + S (O2 + N2)

!
= 1 > 1 < 1

Products

Stoichiometric mixture Rich mixture Lean mixture

11

Any reaction ... :

CH4 + S (O2 + N2) YCH4 Products

Mixture equivalence ratio

YO2

YCH4 YO2

Stoich

MCH 4 S " MO 2 S = = MCH 4 S" S MO 2

CH4 + S (O2 + N2)

Products
12

Air Factor
Any reaction ... :

CH4 + S (O2 + N2)

F=1/

Products

Products

CH4 + F . S (O2 + N2)

13

Air volume (excess)

CH4 + (1+ e ) . S (O2 + N2) Products

e = F - 1 = (1 )/

e= 0 e< 0 e> 0

Stoichiometric mixture Rich mixture Lean mixture

14

CONTENTS
- Some Definitions - Thermodynamics - Chemical kinetics
Arrhenius Law Reaction rate Chemkin

- Reaction mechanism
H2/O2 combustion

- 0-D formulation
Auto-ignition PSR

- Pollutants in atmosphere

15

Thermodynamics
First principle (no variation of kinetic and potential enery) : dU = dQ + dW dW = -PdV dU = dQ -PdV
Constant volume reaction: dQ dW

dU

dU = dQ
Constant pressure reaction: H=U + PV 0

dH=dU + VdP + PdV= dQ + dW + PdV

dH = dQ

16

Thermodynamics

Adiabatic Constant volume reaction:

dW 0 dQ dU

dU = 0

Adiabatic Constant pressure reaction:

dH = 0
17

Thermodynamics
Species enthalpy

chemical

sensible

Mixture enthalpy

18

Thermodynamics

Mixture enthalpy :

chemical with

sensible

19

Initial state - final state

T
final state: 2

initial state : 1

P1 T1 Y1k YCO2

P2 T2 Y2k

If time is infinite Final state = Equilibrium

Gibbs energy: G = H - TS Equilibrium is reached when G is minimal (S is maximal)

20

Thermodynamic Equilibrium
CH4 + 2(O2
+ 3,76

N2)

Final equil. products

At the equilibrium state, burnt gases are composed of: CO2 , H2O , N2 , CO, CH2 , CHi , H, H2 , OH , , O , O2 ,.,.,. , NO , NO2 ,.,.,. Mathematically, the equilibrium composition is obtained by minimizing G
21

Equilibrium burnt gases temperature adiabatic constant pressure : H = cst

N N k k

$# " A
k =1
initial state : 1

$# "" A
k k =1 N

final state: 2

Adiabatic:

The only unknown

1k

"Y
k =1

hk (T1, P ) = "Y2 k hk (T2 , P )

k =1
22

Equilibrium burnt gases temperature adiabatic constant pressure

N T1 1k N 1k

"Y
k =1

hk (T0 , P ) +
N

T0 k =1

$ "Y

c pk (T #, P ) dT # =
T2 N

"Y
k =1

2k

hk (T0 , P ) +

T0 k =1

$ "Y

2k

c pk (T #, P ) dT #

c p 2 (T ")
23

Burnt gases temperature constant pressure

Unknown
T2 T1 p2

T0

#c

(T ") dT " $

T0

#c

p1

(T ") dT " =
N

# (Y
k =1

1k

" Y2 k ) hk (T0 , P )

!
!

Heat released by the combustion

24

c p1 (T, P ) = "Y1k c pk (T, P )

k =1

CO

CO2

25

Burnt gases temperature constant pressure

Assume all cpk = cst = cp and not temperature dependent

c p (T2 " T1 ) = # (Y1k " Y2 k ) hk (T0 )

k =1

Unknown Heat released by the combustion

26

Calorific value
It is the quantity of heat that can theoretically be released per unit mass of fuel Caloric value at constant pressure :
N

( PC ) p = # (Y1k " Y2 k ) hk (T0 , p0 )

k =1

( PC ) p = h1 (T0 , p0 ) " h2 (T0 , p0 )

!
!

Caloric value at constant volume:

( PC ) v = U1 (T0 , p0 ) " U 2 (T0 , p0 )

27

Calorific value
Calorific value: The quantity of heat released by the complete combustion, per unit mass of a fuel, the vapor produced by the combustion of the gas being assumed to remain as a vapour. High calorific value: The amount of heat released by complete combustion, per unit mass of a fuel, the vapor produced by the combustion of the gas being assumed to be completely condensed and its latent heat released.

28

CONTENTS
- Some Definitions - Thermodynamics - Chemical kinetics
Arrhenius Law Reaction rate Chemkin

- Reaction mechanism
H2/O2 combustion

- 0-D formulation
Auto-ignition PSR

- Pollutants in atmosphere

29

Reacting mixture

Temperature

Collisions

Reaction
30

Collision frequency
Motion molecular velocity

Kuo, 2005

Volume through which the molecule sweeps in 1s For one molecule (if all other molecules are motionless)
31

Collision frequency

32 Kuo, 2005

Collision frequency

A+A A+B 2A + 3B

P P P
2 2 3

But all collisions do not lead to reaction

33

Arrhenius Law Only molecules with E > Ea will react ...

Ea =Activation Energy Svante Arrhenius (1859-1927)

dCB = " fc P e dt
collision frequency

Ea " RT

Boltzmann factor

steric factor (depends on the orientation of the colliding molecules)

with
R
34

Order of reaction
N N k k

$# " A
k =1

$# "" A
k k =1 N k =1

dCM k ! ! dt

= (# " k" $ # " k) kf

% (C

Mk

#" k

Overall order of reaction :

m = $# " k
k =1
35

First order reactions

! Valid only for elementary reactions

36

Second order reactions

AB

37

Third order reactions

Third order reactions

--> Becomes a 2nd order reaction if CM is cst 38

Consecutive reactions
k1

k2

39

Parallel reactions
Twin reactions

A+B " "# C k2 A+B " "# D

dCC = k1 CA CB dt
dCD = k2 CA CB dt

k1

CC k1 " = CD k2
40

Parallel reactions
Competitive reactions

A+B " "# C k2 A+ E " "# D

dCC = k1 CA CB dt
dCD = k2 CA CE dt

k1

CE 0 k1 " ln = ln CB 0 # CC k 2 CE 0 # CD
41

CB 0

Opposing (or reverse) reactions

% %& $# "k Ak ' % % k =1 kb

kf

$# "" A
k k =1

42

Opposing (or reverse) reactions But complex mechanisms: N species, I reactions :

% %& $# "k,i Ak ' % % k =1 kb

Each reaction

kf

$# ""
k =1

k ,i

Ak

for i = 1,....., I
qi

is characterized by a rate of progress

43

General expression of reaction rates

Reaction rate of species k in the ith reaction is:

Reaction rate of species k for the overall mechanism is:

.
44

General expression of reaction rates

Molar reaction rate:

dCk = "k dt

# mole & % 3 ( m s' $ # kg & % 3 ( $ m s'

dCk M k = Mk "k dt !
as

Ck M k = " k = " Yk

!
!

d"Yk = Mk #k dt

Mass reaction rate

45

General expression of reaction rates

d"Yk = Mk #k dt

!
Then:

d"Yk # dt = # M k $ k k =1 k =1
N k

# M "k = 0
k =1

Conservation of mass
46

CHEMKIN
Kinetics Scheme Thermodynamics Data Base Set of CHEMKIN Routines : CKXTY CKYTX CKXTC CKCPY CKWXP CKWYP . .

CHEMKIN Interpreter

LINK file

Users program (x. : equil, .)

47

CONTENTS
- Some Definitions - Thermodynamics - Chemical kinetics
Arrhenius Law Reaction rate Chemkin

- Reaction mechanism
H2/O2 combustion

- 0-D formulation
Auto-ignition PSR

- Pollutants in atmosphere

48

DETAILED CHEMISTRY

H2 + 1/2 O2 CH4 + 2O2

H2O CO2 +2 H2O

CH4 + 2 O2

Products

Even at the equilibrium state, burnt gases are composed of: CO2 , H2O , CO, CH2 , CHi , H, H2 , OH , , O , O2 ,.,.,.,.,.,.
49

Chain reactions
Series of competitives, consecutives and opposing reactions Apparition of intermediate species Importance of free radicals Radicals: highly reactive molecules or atoms
A2 + M " 2 A + M
Chain-initiation reaction (A2 has a lower Ea than B2) Chain-carrying reactions: radical -> radical (fast propagation)

A + B2 " AB + B B + A2 " AB + A A + AB " A2 + B B + AB " B2 + A

2 A + M " A2 + M 2 B + M " B2 + M

Chain terminating reaction

50

H2 / O2 combustion

51

DETAILED CHEMISTRY (H2 - O2 combustion)

Temperature Collisions Chain-Initiating reactions

O2 + M H2 + M

2O +M 2H +M

M denotes all other species as third body (O2, H2O, ) Delivering its energy to O2 and H2 helping them to dissociate

INITIATION : free - radical production

52

DETAILED CHEMISTRY
Chain-branching reaction : Radicals are more produced than consumed
O + H2 H + O2 H + OH O + OH

Very fast reactions

53

Example :
A 1 cm3 container with n =1019 molecules and fc = 108 collisions / s 1 free radical per cm3

Chain-carrying: time for all molecules to react = 1019/108 = 30,000 years

54

Chain reactions

Assume chain-branching reactions 1 radical --> 2 radicals

Chain-branching: 1 + 2 + 22 + + 2L= (2L+1-1)/(2-1) = 1019 molecules after L=64 generations Time to react = 64 / 108 1 s
Extremely fast reaction ....

If 1% of the reactions are chain-branching: t 40 s

55

DETAILED CHEMISTRY
Chain-carrying : Radicals and final products

OH + H2 O + H2O

H2 O + H 2 OH

56

DETAILED CHEMISTRY
Chain-terminating steps : recombination mechanism
H+H+M O+O+M H+O+M H + OH + M H2 + M O2 + M OH + M H2O + M
57

COMBUSTION of H2 / O2
H2 + O2 H2 + OH O + OH O + H2 H + O2 +M OH + HO2 H + HO2 O + HO2 OH + OH H+H+M H + H + H2 H + H + H2O H + OH + M . . 2 OH H2 O + H H + O2 OH + H HO2 + M H 2 O + O2 2 OH O2 + OH O + H2O H2 + M H2 + H2 H2 + H2O H2 O + M

>10 species >40 reactions

58

COMBUSTION of CH4 / O2
C2H6 CH4 CH3 CH2O HCO CH CO CO, CO2
59

C3... C3...

C2H5 C2H4 C2H3 C2H2 CH2

OXYDATION of CO
Chain-terminating steps:
CO + OH CO + O2 CO2 + H CO2 + O 2 OH OH + O

Main OH production reactions:

O + H2O H + O2

At the flame front:

CO + HO2 CO2 + OH
60

CONTENTS
- Some Definitions - Thermodynamics - Chemical kinetics
Arrhenius Law Reaction rate Chemkin

- Reaction mechanism
H2/O2 combustion

- 0-D formulation
Auto-ignition PSR

- Pollutants in atmosphere

61

Application of spontaneous combustion

Hypersonic combustion (SCRAMJET) Diesel engines To be avoided in : Safety characteristic length of fuel tanks Semenov theory Spark ignition engines (avoid pinking)

62

Spontaneous combustion

Adiabatic, constant pressure

63

Auto-ignition of a reactive mixture

Adiabatic, constant pressure

Initial conditions :
64

Auto-ignition of a reactive mixture

Auto-igniting delay time

T0 > Ti

65

Auto-ignition delay time i decreases exponentially with T0

i ms
40

CH4
10

C2H2 CO H2

Kerosene

1 0.5 1100

T C
1000 900 800 700 600

i changes as P01-n Inuence of equivalence ratio and dilutant66(YN2)

Spontaneous combustion
T = ambient: metastable state, reaction rate is almost null When T increases: If T > Ti Beginning of exothermic oxidation reaction: production of enough radicals to ignite If T < Ti Heat released is not sufcient to increase the temperature, because endothermic reactions absorb the heat to crack the fuel: not enough radicals are produced to ignite
67

Spontaneous combustion
Container with constant volume with isothermal wall (Tw) and a wall surface S
S Tw YO Heat losses Q Container balance energy equation .
68

V YF

Spontaneous combustion
d"VYk = V Mk #k dt d"VU = # K S (T # Tw ) dt

U = " YkU k
k =1

dU k dYk # (" VYk dt + U k " V dt ) = $ K S (T $ Tw ) k =1 ! N dU k $ (" VYk dt + U kV M k # k ) = % K S (T % Tw ) k =1

69

Spontaneous combustion
dT " V cv = # % (V M k U k $ k ) # K S (T # Tw ) dt k =1 N

dT " V cv = V # F Qv 0 $ K S (T $ Tw ) dt

Production

Heat loss

Fuel consumption rate modeling:

70

Semenov theory
Auto-ignition conditions

Production >

Heat loss

" F Qv 0

S # K (T $ Tw ) V

y1 (T )
!

y 2 (T )
71

y(T)

" F Qv 0
Production (chemical)

Y1(T)

T
72

Y (T)

Y2 (T) Heat loss

S K (T " Tw ) V

Tw

T
73

y1 y 2

Case 1: T0 high,

Tw

Auto-ignition

74

y1 y 2

Case 2: two curves are tangent

Tw

Tc

If T < Tc,

The temperature increases up to T=Tc dT/dt =0 (unstable) T = Tc + , Ignition

If T > Tc,

Auto-ignition
75

y2 y

y1

Case 3: a If T < Ta , the temperature increases up to Ta and remains stable

Tw T

If Ta < T < Tb , the temperature decreases to Ta and remains stable If T > Tb, Auto-ignition
76

Varying K or (S/V)
The critical temperature Tc is not an intrinsic mixture property. Indeed, it is function of K and (S/V)

K (S/V) Tw T

If the system is well insulated, K decreases, and it increases the risk of auto-ignition S/V=1/L If L goes up, S/V decreases and it Increases the risk of auto-ignition 77

Varying P

w There exists a critical pressure Pc above which there is always mixture auto-ignition.
78

Determination of ignition limits (Pi, Ti)

y y1 y 2

Y1 = " F Qv 0
C

S Y2 = K (T " Tw ) V
T

Tw

Ti

At the critical point C:

!
79

One shows that:

80

Determination of ignition limits (Pi, Ti)

Ignition

no combustion
Lean limit Rich limit

Equivalence ratio

Ignition

no combustion
Lean limit Rich limit
81 Equivalence ratio

Determination of ignition limits (Pi, Ti)

Ignition

no combustion

82

Hydrocarbons ignition limits

83

Inuence of T0 on ignition (C7H16-air)

Temperature (K)

Time (s)

P0 =30 bars, =0.5

84

Inuence of T0 on ignition (C7H16-air)

Cold ame Principal ignition

Ignition delay (s)

Initial temperature (K)

P0 =30 bars, =0.5

85

CONTENTS
- Some Definitions - Thermodynamics - Chemical kinetics
Arrhenius Law Reaction rate Chemkin

- Reaction mechanism
H2/O2 combustion

- 0-D formulation
Auto-ignition PSR

- Pollutants in atmosphere

86

Perfectly stirred reactor (PSR)

Yk , hk, T Volume V INLET m , Yk0 , hk0, T0 Yk , hk, T OUTLET

!
Feed at the inlet at the state: X0 Homogeneous combustion Burnt gases at the outlet

Residence time

Species mass balance equation :

IN OUT PRODUCTION .

. dYk "V = m Yk 0 # m Yk + $ k M k V dt

k = 1,..., N

88

Enthalpy balance:

dh "V = m #Yk 0 hk 0 $ m #Yk hk $ Qh dt k =1 k =1

N

with h =

"Y
k =1

hk

" dhk % dh = ($Yk ' + dt k =1 # dt &

" dYk % hk ' ($ # dt & k =1

N

! !
!

dhk dT = C pk dt dt

C p = "Yk C pk
k =1

dh dT = Cp + dt dt !

dYk " hk dt k =1

89

Enthalpy balance:

dT " V Cp = m #Yk 0 hk 0 $ m #Yk hk $ Qh dt k =1 k =1

%N dYk ( $ '# hk " V * dt ) & k =1

dYk "V = m Yk 0 # m Yk + $ k M k V dt

dT " V Cp = m #Yk 0 hk 0 $ m #Yk hk $ Qh dt k =1 k =1

& N ) $ m #Yk 0 hk + m #Yk hk + ($#V 90hk % k M k + ' k =1 * k =1 k =1

N N

Balance Equations
dYk "V = m Yk 0 # m Yk + $ k M k V dt

k = 1,..., N

N & ) dT " V Cp = m #Yk 0 hk 0 $ m #Yk 0 hk $ Qh + V ( $# hk % k M k + dt ' k =1 * k =1 k =1 N N

Heat release rate

h
91

ATTENTION

dT " V Cp = m #Yk 0 hk 0 $ m #Yk hk $ Qh + h dt k =1 k =1 N N

dT " V Cp = m #Yk 0 hk 0 $ m #Yk 0 hk $ Qh + h dt k =1 k =1

dh "V = m #Yk 0 hk 0 $ m #Yk hk $ Qh dt k =1 k =1

92

Application example
dYk 1 $k Mk = (Yk 0 # Yk ) + dt " %
dT 1 1 Cp = #Yk 0 hk 0 $ dt " k =1 "
N N

k = 1,..., N

!
!

Qh h #Yk 0hk $ %V + % k =1

at t=0 , Yk(0)=Yk0 , T(0) = Ti

Volume V Outlet Yk (t), hk (t), T(t)
93

T0 = 300 K

Inlet

H2/Air mixture Pressure= 1 atm

Stoic. H2/Air T0 = 300 K Pressure= 1 atm

Ti = 4000K

=0,01 s

94

Influence of
Ti = 4000K

Time (s)

95

Influence of
Ti = 4000K

Time (s)

96

Influence of
Ti = 4000K

Residence time (s)

97

Influence of Ti

=0,01 s

Time (s)

98

Influence of Ti

=0,01 s

Time (s)

99

CONTENTS
- Some Definitions - Thermodynamics - Chemical kinetics
Arrhenius Law Reaction rate Chemkin

- Reaction mechanism
H2/O2 combustion

- 0-D formulation
Auto-ignition PSR

- Pollutants in atmosphere

100

 CO2, H2O CO

(vegetations, combustion) CH4 (Rice, Ruminants., combustion) CHx Soot NOx (Lightning, combustion) COV (combustion) SOx Cl Br. .. ..
101

Impact of Pollutants on the atmosphere

102

Troposphere : Altitude < 10-15 km, T 220K

NO2 O2 + O +M NO + O3 k1 k2 k3 day NO + O O3 + M NO2 + O2 k1 (h) k2 very fast

> !

night

=> Fragile equilibrium Production of O3

If steady state for NO:

O3

k1 C NO

k3 C NO

If NO decreases and NO2 increases : Increase of O3

Effect of CO
CO + OH CO2 + H H + O2 + M OH2 + M
Importance of OH : Initiation of the process

104

Effect of CO
If [O3] / [NO] < 5000
HO2 + NO NO2 + OH
NO2 + h NO + O O2+O+M O3 +M
( > 420 nm)

If [O3] / [NO] > 5000

HO2 + O3 OH + 2 O2

Balance : CO +2 O2 CO2 + O3

Balance : CO + O3 CO2 + O2

Formation of O3

Destruction of O3
105

Effect of CH4
CH4 + OH CH3 + H2O CH3 + O2 + M CH3O2 + M CH3O2 + NO CH3O + NO2 CH3O + O2 CH2O + HO2 CH2O + O2 HCO + HO2 2 HO2 + 2 NO 2 NO2 + 2 OH HCO + OH CO + H2O
3NO2 + h 3NO + 3O ( > 420 nm) 3O2+3O+3M 3O3 +3M 20% 106 - 50% of CO in atmosphere

Balance : CH4+ 6 O2 CO + 2 H2O + 3 O3

NO - NO2 Photochemical Cycle

Day time Solar radiation allows formation of O Formation of O3 (O + O2) Produced NO reacts with O3 and forms O2 et NO2 Establishment of equilibrium Night no production of O Consumption of O3 by NO emitted by cars (unless the wind has moved O3 away)

< 420nm

NO2

NO

O2 O3

O2

107

NO - NO2 Photochemical Cycle in polluted atmosphere

Day time New mechanism of NO2 / RH formation No consumption of O3 Continuous increase of O3
O

< 420nm

NO2 RO2 O2 O3

NO +RH

O2

Night no production of O Consumption of O3 by NO emitted by cars (unless the wind has moved O3 away)
108

Troposphere : < 10-15 km, T

acid rain
NO2 + OH HNO3

220K

Stratosphere : > 10-15 km, T

Ozone layer : O2 k1 2 O O3

270K

k1 (h)

O + O2

Destruction of O3 by X : NO, OH, Cl, Br, .....

X + O3 XO + O O3 + O XO + O2 X + O2 2 O2

Direct Effects of NOx on atmospheric equilibrium

NOx participate in the formation of ozone in the troposphere : Smog NOx participate in the destruction of the ozone layer in the stratosphere

111